Electrocarboxylation of CCI4 in MeCN during electrolysis with the sacrificial Zn anode
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The regularities of galvanostatic electrocarboxylation of CCl4 in Alk4NBr/MeCN in an undivided cell with sacrificial Zn anode were studied. The major product of the electrolysis is zinc trichloroacetate, which is formed as a result of the reaction of the cathode-generated CCl3- anion with CO2. The further trichloroacetate reduction is prevented by cathode passivation. Therefore, small amounts of zinc dichloro- and monochloroacetates are formed due to the chemical reduction of zinc trichloroacetate with Zn0 rather than the cathodic reduction. Zero-valence zinc is formed in minor amounts when Zn2+ ions are discharged at the cathode surface because of the low solubility of ZnBr2 in MeCN. The treatment of (Cl3CCOO)2Zn with H2SO4 in MeOH gives Cl3CCO2Me in 11% yield based on the starting CCl4.
Key wordselectrochemical carboxylation sacrificial zinc anode tetrachloromethane carbon dioxide trichloroacetic acid
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- 1.B. L. Sigacheva, V. A. Frolovskii, V. A. Petrosyan, Elektro-khimiya, 2005, 41, 1133 [Russ. J. Electrochem. (Engl. Transl.), 2005, 41].Google Scholar
- 2.J. Chaussard, J.-C. Folest, J. Y. Nedelec, J. Perichon, S. Sibille, M. Troupel, Synthesis, 1990, 369.Google Scholar
- 3.G. Silvestry, S. Gambino, G. Filardo, NATO ASI Ser., Ser. C, 1987, 339.Google Scholar
- 4.V. G. Koshechko, V. D. Pokhodenko, Teor. Eksp. Khim., 1997, 33, 268 [Theor. Exp. Chem. (Engl. Transl.), 1997, 33].Google Scholar
- 9.A. J. Gordon, R. A. Ford, The Chemist’s Companion, Wiley, New York—London—Sidney—Toronto, 1972.Google Scholar